WO2010072192A2

WO2010072192A2 - Security and/or valuable document comprising a conductive structure and method for producing same

Info

Publication number: WO2010072192A2
Application number: PCT/DE2009/001717
Authority: WO
Inventors: Oliver Muth; Michael Hagemann; Manfred Paeschke; Peter Fleischer; Eckhardt Wefringhaus
Original assignee: Bundesdruckerei Gmbh
Priority date: 2008-12-23
Filing date: 2009-12-04
Publication date: 2010-07-01
Also published as: CN102264946A; DE102008063030A1; CN102264946B; WO2010072192A3; EP2367966A2; EP2367966B1

Abstract

The invention relates to a method for producing a layer that is conductive for electric current on a substrate, comprising the following method steps: a) a coating composed of a first formulation, which contains an organic binder, an aqueous or organic solvent and electrically conductive particles, is applied to the substrate, b) the substrate with the coating is subjected to a drying method stage, wherein the solvent is removed, c) the substrate with the dried coating is treated with a second formulation for autocatalytic electroless metal coating. The invention furthermore relates to a conductive structure obtainable in this way, and to a security and/or valuable document comprising such a conductive structure.

Description

Security and / or value document with a conductive structure and method for its production

Field of the invention

The invention relates to a method for producing a layer capable of conducting electric current on a substrate with the following method steps: a coating of a first layer is applied to the substrate

Preparation containing electrically conductive particles, the substrate with the coating is treated with a second preparation for autocatalytic electroless metal coating. The invention further relates to a conductive structure and a security and / or valuable document having such a conductive structure.

Prior art and background of the invention.

Security and / or value documents, such as identity cards, passports, ID cards, access control cards, visas, tickets, driver's licenses, motor vehicle papers, personalized securities

Credit cards, or personalized smart cards, increasingly have electronic circuits, and other active and passive electronic components, such as integrated semiconductors (ICs), but also chip modules, displays, batteries, coils, capacitors,

Contact points, etc., on. In this connection it is often necessary, on or within the security and / or value document conductive structures (conductive structures), such as interconnects to set up, which electrically connect electronic components with each other or even perform independent functions within a circuit. The latter is given, for example, in the case of an RFID antenna.

The production of such conductive structures can be done in various ways. It is known

Apply preparations with electrically conductive particles on a substrate. The application can be done for example by means of known printing technologies. Lead structures produced in this way have a relatively low

Conductivity, compared with structures made of metallic materials. This interferes with, among others, in terms of disturbing Ohm ^'sche losses, lower inductance, lower quality and high Ansprechfeldstärken. An advantage of printing a conductive structure in particular

Substrates made of organic polymer materials is that a good bond between substrate and conductive structure is formed on the basis of organic polymers used in printing inks binders.

Furthermore, it is known to produce conductive structures on non-conductive substrates by depositing a metal autocatalytically and electrolessly directly onto the substrate or after previously depositing a so-called seed layer (English: seed layer). For this purpose, in detail, for example, to the reference WO 2006/065221 Al referenced. The seed layer is typically very thin, usually 1 - 3 microns, and the deposited metal film is many times thicker, usually 5 - 50 microns, as the seed layer. In this technology, the bond between seed layer and substrate on the one hand and between deposited metal layer and seed layer on the other hand is problematic. While this is not necessarily a problem in the case of rigid substrates, such as silicon substrates, however, significant problems arise in the case of flexible substrates, such as films of organic polymer materials, as used in the field of security and / or value documents.

Technical problem of the invention

The invention is therefore based on the technical problem of specifying a method for producing a conductive electrical layer layer on a substrate security and / or value document, wherein the conductive layer forms a good bond with the substrate and at the same time has an improved conductivity.

Broad features of the invention and preferred embodiments To solve this technical problem, the invention teaches methods for producing a layer conductive for electrical current on a substrate with the following method steps: a) a coating of a first preparation is applied to the substrate, which is an organic binder, a wassπges or organic solvent and Contains particles, b) the substrate with the coating becomes one

C) the substrate with the dried coating is treated with a second preparation for autocatalytic electroless metal plating.

The invention is based on the recognition that in the course of the drying process stage, the solvent from the

Coating is driven off, wherein the coating between the particles and m of Bmdemittelmatnx forms a pore system with interconnected open pores. Depending on the proportion of solvent m in the first preparation, the volume fraction of the pores is large or small. In the extreme case of the maximum porosity, the electrically conductive particles are surrounded by a thin layer of the binder, wherein the particles m contact areas are connected or bonded together and with the substrate. The porosity then corresponds to the core of a loose Schuttuhg the particles. It is essential for the invention that in step c) a deposition takes place not only on the outer surface of the coating, but also on inner surfaces, namely in the pore spaces. The pores become as it were filled with deposited metal and form a network of metal. As a result, a conductive structure is obtained which has the conductivity of the metal used, but exhibits a very good adhesion to the substrate due to the binder matrix.

The open porosity of the coating after stage b) and before stage c), measured by the mercury method or the xylene method, is typically in the range of 0.005 to 0.45, usually 0.02 to 0.10.

While any material is fundamentally suitable as the substrate, in the context of security and / or value documents it is preferred if it is an organic polymer, preferably selected from the group consisting of "PC (polycarbonate, especially bisphenol A polycarbonate), PET

(Polyethylene glycol terephthalate), PET-G, PET-F, PMMA (polymethyl methacrylate), ABS (acrylonitrile-butadiene-styrene), PE (polyethylene), PP (polypropylene), PI (polyimide or poly-trans-isoprene), PVC (polyvinyl chloride ) and

Copolymers of such polymers. "In particular, PC is preferred because of its other advantageous properties known in this technological field.

The substrate may then be, for example, a film or a foil composite of a security and / or value document, in particular an identity card, passport, ID card, access card, visa, ticket, driver's license, motor vehicle paper, personalized security, credit card, or personalized chip cards, be. Basically, any electrical function can be realized with conductive layers. For example, conductor tracks can be designed and configured for the "wired" transmission of electrical signals and / or electrical energy, but a conductive layer can also be a coil structure, more particularly an antenna structure, in particular an antenna structure which is part of an RFID circuit ,

The binder contained in the first preparation may in principle be any of the coating technology, including paint technology and printing technology, commonly employed binder or binder compound, the skilled artisan will readily select a binder suitable and compatible with a particular substrate material. Also, the proper choice of composition of the first formulation, which can be readily made by one skilled in the art, will depend on the type of application, for example on the printing technology used.

Typical layer thicknesses of a coating of stage a) are in the range of 0.5-100 .mu.m, in particular 5-50 .mu.m, usually 10-30 .mu.m.

A suitable binder, for example, a polycarbonate derivative based on a gem-disubstituted Dihydroxydiphenylcycloalkans, which may have a weight average molecular weight of at least 10,000, preferably from 20,000 to 300,000. In particular, the polycarbonate derivative may contain functional carbonate structural units of the formula (I)

(I ^'

wherein R ¹ and R ² are independently hydrogen, halogen, preferably chlorine or bromine, Ci-Cg-alkyl, C ₅ -C ₆ - cycloalkyl, C ₆ -Cio-aryl, preferably phenyl, and C ₇ -C ₂ - aralkyl, preferably phenyl-Ci-Cj-alkyl, in particular benzyl; m is an integer from 4 to 7, preferably 4 or 5; R ³ and R ^{4 are} individually selectable for each X, independently of one another hydrogen or C ₁ -C ₆ -alkyl; X is carbon and n is an integer greater than 20, with the proviso that on at least one atom X, R ³ and R ^{4 are} simultaneously alkyl. It is further preferred if X, R ³ and R ^{4 are} simultaneously alkyl at 1 to 2 atoms, in particular only at one atom. R ³ and R ⁴ may be in particular methyl. The X atoms in the alpha position to the diphenyl-substituted C atom (Cl) can not be dialkyl-substituted. The X atoms in beta position to Cl can be disubstituted with alkyl. Preferably, m = 4 or 5. The polycarbonate derivative can be prepared, for example, on the basis of monomers, such as 4,4 '- (3,3,5-trimethylcyclohexane-1,1-diyl) -diphenol. 4,4 ^' - (3,3 dimethylcyclohexane-1,1-diyl) diphenol, or 4,4 '- (2,4,4-trimethylcyclopentane-1,1-diyl) diphenol. Such a polycarbonate derivative can be prepared, for example, according to the document DE 38 32 396.6 from diphenols of the formula (Ia), the disclosure of which is hereby incorporated in full in the disclosure of this description. It is possible to use both a diphenol of the formula (Ia) to form homopolycarbonates and a plurality of diphenols of the formula (Ia) to form copolycarbonates (meaning of radicals, groups and parameters, as in formula I).

(Ia)

In addition, the diphenols of the formula (Ia) may also be mixed with other diphenols, for example those of the formula (Ib)

HO - Z - OH (Ib), be used for the preparation of high molecular weight, thermoplastic, aromatic polycarbonate derivatives. Suitable other diphenols of the formula (Ib) are those in which Z is an aromatic radical having 6 to 30 C atoms, which may contain one or more aromatic nuclei, may be substituted, and aliphatic radicals or cycloaliphatic radicals other than those of the formula (II) Ia) or heteroatoms may contain as bridge members. Examples of the diphenols of the formula (Ib) are: hydroquinone, resorcinol, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ether, bis (hydroxyphenyl) ether, bis (hydroxyphenyl) ether, (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, alpha, alpha 'bis (hydroxyphenyl) diisopropylbenzenes and their nuclear alkylated and nucleated compounds. These and other suitable diphenols are described, for example, in US Pat. Nos. 3,028,365, 2,999,835, 3,148,172, 3,275,601, 2,991,273, 3,271,367, 3,062,781, 2,970,131 and 2,999,846, in US Pat the

References DE-A 1 570 703, 2 063 050, 2 063 052, 2 211 956, FR-A 1 561 518 and in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964", which are hereby incorporated in full in the disclosure of the present application. Preferred other diphenols are, for example: 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1, 1-bis- ( 4-hydroxyphenyl) -cyclohexane, alpha, alpha -bis (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis (3-methyl-4-) hydroxyphenyl) -propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-Bxs- (3, 5- dimethyl-4-hydroxyphenyl) -propane, bis (3, 5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,1 Bis- (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, alpha, alpha -bis (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis (3,5) dichloro-4-hydroxyphenyl) -propane and 2, 2-bis (3, 5-dibromo-4-hydroxyphenyl) -propane. Particularly preferred diphenols of the formula (Ib) are, for example: 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2-bis - (3, 5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane and 1,1-bis (4-hydroxyphenyl) -cyclohexane. In particular, 2, 2-bis (4-hydroxyphenyl) propane is preferred. The other diphenols can be used both individually and in a mixture. The molar ratio of diphenols of the formula (Ia) to the optionally used other diphenols of the formula (Ib) should be between 100 mol% (Ia) to 0 mol% (Ib) and 2 mol% (Ia) to 98 mol -% (Ib), preferably between 100 mol% (Ia) to 0 mol% (Ib) and 10 mol% (Ia) to 90 mol% (Ib) and especially between 100 mol% (Ia) to 0 mol% (Ib) and 30 mol% (Ia) to 70 mol% (Ib). The high molecular weight polycarbonate derivatives of the diphenols of the formula (Ia), optionally in combination with other diphenols, can be prepared by the known polycarbonate production processes. The various diphenols can be linked together both statistically and in blocks. The polycarbonate derivatives used accordingly can be used per se be branched known manner. If the branching is desired, by condensing small amounts, preferably amounts between 0.05 and 2.0 mol% (based on diphenols used), of trifunctional or more than trifunctional in a known manner

Compounds, especially those having three or more than three phenolic hydroxyl groups, can be achieved. Some branching agents having three or more than three phenolic hydroxyl groups are: phloroglucinol, 4,6-dimethyl-2,4,4-tris (4-hydroxyphenyl) -hepten-2, 4, β-dimethyl-2, 4, 6 tri- (4-hydroxyphenyl) heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) - phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenyl-isopropyl) -phenol, 2, 6-is- (2 -hydroxy-5-methyl-benzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane, hexa- [4- (4-hydroxyphenyl-iso-propyl) -phenyl] - orthoterephthalic acid ester, tetra (4-hydroxy-phenyl) -methane, tetra- [4- (4-hydroxyphenyl-isopropyl) -phenoxy] -methane and 1,4-bis- [4 ', 4 "-dihydroxytriphenyl) -methyl] -benzene , Some of the other trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole. As chain terminators known per se regulation of the molecular weight of the polycarbonate derivatives are monofunctional compounds in conventional concentrates. Suitable compounds are, for example, phenol, tert-butylphenols or other alkyl-substituted phenols. For controlling the molecular weight, in particular small amounts of phenols of the formula (Ic) are suitable

(I c) wherein

R is a branched C ₈ - and / or C ₉ -alkyl radical. Preferably, in the alkyl radical R, the proportion of Ci-1 ₃ protons between 47 and 89% and the proportion of CH and CH ₂ - protons between 53 and 11%; Also preferred is R m o- and / or p-position to the OH group, and more preferably the upper limit of the ortho-portion is 20%. The chain terminators are generally used in amounts of 0.5 to 10, preferably 1.5 to 8 mol%, based on diphenols used. The polycarbonate derivatives may preferably be prepared in a manner known per se according to the phase boundary behavior (compare H. Schnell "Chemistry and Physics of Polycarbonates", Polymer Reviews, Vol. IX, page 33 et seq., Interscience Publ. In this case, the diphenols of the formula (Ia) are dissolved in an aqueous alkaline phase. For the preparation of copolycarbonates with other diphenols, mixtures of diphenols of the formula (Ia) and the other diphenols, for example those of the formula (Ib), are used. To regulate the molecular weight, chain terminators of, for example, the formula (Ic) can be added. Then, in the presence of an inert, preferably polycarbonate losenden, organic phase reacted with phosgene by the method of interfacial condensation. The reaction temperature is between ^{0 0} C and 40 ⁰ C. The optionally used branching agents (preferably 0.05 to 2.0 mol%) can either be initially charged with the diphenols in the aqueous alkaline phase or added dissolved in the organic solvent prior to phosgenation. In addition to the diphenols of the formula (Ia) and, if appropriate, other diphenols (Ib), their mono- and / or bis-chlorocarbonic acid esters may also be used, these being added dissolved in organic solvents. The amount of chain terminators and branching agents then depends on the molar amount of

/ 10 diphenolate residues corresponding to formula (Ia) and optionally formula (Ib); When using chloroformates the amount of phosgene can be reduced accordingly in a known manner. Suitable organic solvents for the chain terminators and optionally for the branching agents and the chloroformates are, for example, methylene chloride, chlorobenzene, in particular mixtures of methylene chloride and chlorobenzene. Optionally, the chain terminators and branching agents used can be dissolved in the same solvent. As an organic phase for the interfacial poly

/ condensation serves, for example, methylene chloride,

Chlorobenzene and mixtures of methylene chloride and chlorobenzene. The aqueous alkaline phase used is, for example, NaOH solution. The preparation of the polycarbonate derivatives by the interfacial process can be catalyzed in a conventional manner by catalysts such as tertiary amines, in particular tertiary aliphatic amines such as tributylamine or triethylamine; the catalysts can be used in amounts of from 0.05 to 10 mol%, based on moles of diphenols used. The catalysts can be used before starting the Phosphatization or during or after the Phosgemerung be added. The polycarbonate derivatives can be prepared by the known method in a homogeneous phase, the so-called "Pyπdinverfahren" and by the known melt transesterification using, for example, diphenyl carbonate instead of phosgene. The polycarbonate derivatives may be linear or branched, they are homopolycarbonates or copolycarbonates based on the diphenols of the formula (Ia). By arbitrary composition with other diphenols, in particular with those of the formula (Ib), the polycarbonate properties can be varied in a favorable manner. In such copolycarbonates, the diphenols of the formula (Ia) are present in amounts of from 100 mol% to 2 mol%, preferably in amounts of from 100 mol% to 10 mol% and in particular in amounts of from 100 mol% to 30 mol% %, based on the total amount of 100 mol% of Diphenolemheiten contained in Polycarbonatedeπvaten. The polycarbonate derivative is, for example, a copolymer containing, in particular consisting of, monomer units M1 based on the formula

(Ib), in particular bisphenol A, and monomer units M2 based on the geminally disubstituted dihydroxydiphenylcycloalkane, preferably of the 4,4 - (3, 3, 5-trimethylcyclohexan-l, 1-diyl) diphenol, wherein the molar ratio of M2 / M1 is preferably greater than 0.3, in particular greater than 0.4, for example greater than 0.5.

As a solvent of the first preparation come in addition to water all common in coating technology organic solvents and solvent mixtures, including with water, in Question. By way of example only, preferably halogen-free organic solvents may be mentioned. Suitable compounds include aliphatic, cycloaliphatic, aromatic hydrocarbons, such as mesitylene, 1,2,4-trimethylbenzene, cumene and solvent naphtha, toluene, xylene; (organic) esters such as methyl acetate, ethyl acetate, butyl acetate, methoxypropyl acetate, ethyl 3-ethoxypropionate, butyglycol acetate. Preference is given to mesitylene, 1,2,4-trimethylbenzene, cumene and solvent naphtha, toluene, xylene, methyl acetate, ethyl acetate,

Methoxypropyl acetate, ethyl 3-ethoxypropionate, mono- or polyvalent C 1 -C 10 -alkyl, cycloalkyl, aryl- (C 6 -C 10), or aralkyl alcohols (C 6 -C 10), linear or branched. Most particularly preferred are: mesitylene (1,3,5-trimethylbenzene), 1,2,4-trimethylbenzene, cumene (2

Phenylpropane), solvent naptha and ethyl 3-ethoxypropionate. A solvent mixture suitable for the above-described binder in detail comprises, for example, A) 0 to 10% by weight, preferably 1 to 5% by weight, in particular 2 to 3% by weight, mesitylene, B) 10 to 50% by weight. %, preferably 25 to 50 wt .-%, in particular 30 to 40 wt .-%, l-methoxy-2-propanol acetate, C) 0 to 20 wt .-%, preferably 1 to 20 wt .-%, in particular 7 to 15% by weight, 1, 2, 4-trimethylbenzene, D) 10 to 50% by weight, preferably 25 to 50% by weight, in particular 30 to 40% by weight, of ethyl 3-ethoxypropionate, E) 0 to 10 wt .-%, preferably 0.01 to 2 wt .-%, in particular 0.05 to 0.5 wt .-%, cumene, and 0 to 80 wt .-%, preferably 1 to 40 wt. %, in particular 15 to 25 wt .-%, solvent naphtha, wherein the sum of the components A) to E) always gives 100 wt .-%. The first preparation preferably contains a proportion of solvent, preferably organic solvent, of from 2 to 30% by weight, in particular from 4 to 10% by weight, based on the total weight of the preparation.

The particles of the first preparation may in principle also have any composition. They may be inorganic non-metallic or metallic particles, for example metal oxides such as SiO 2 or TiO 2, carbon black, silver, gold, titanium, tin, palladium, copper or other inorganic fillers known in coating technology. However, it is also possible to use polymer particles, for example those known in coating technology as organic fillers.

The first preparation preferably has a fraction of 30-99% by weight, in particular 70 to 95% by weight, of particles, preferably electrically conductive particles, in particular metal particles, for example silver particles.

In the context of the invention, it is preferred if the particle size is at least 90%, based on the volume, of the particles used in the range between 0, 1 and 30 .mu.m, in particular between 2 and 20 microns. The particle size distribution can be monomodal, but it can also be set up mixtures of particles of different particle sizes or particle size distributions. For example, in conjunction dlO values of 0.5 to 5 .mu.m and d90 values of 5 to 30 .mu.m can be set up. Particle size and particle size distributions, including d10 and d90 values, can be determined by static laser diffraction methods, for example with an LS Particle Size Analyzer

(Beckmann Coulter) according to standard procedures and standard evaluation software.

Suitable finished first preparations are, for example, well-known preparations such as Conductor Paste DuPont 5029 or 5028 or 5033.

The application of the first preparation can be carried out with all well-known printing processes (for example through-, gravure-, portrait- and planographic printing but also inkjet printing, in particular screen printing). However, other application methods customary in coating technology, such as spraying, brushing, knife coating, dipping, etc. can also be used. Preference is given to screen printing and stencil printing.

The stage b) can be carried out for 0.1 to 100 mm., In particular 1 to 30 mm., At 30 - 200 ⁰ C, in particular 60 to 130 ° C. It is possible in the context of stage b) also in place of the heating or in addition to a negative pressure, for example in the range of 10 to 800 mbar (absolute), in particular 100 to 600 mbar set up.

The second preparation may be a wet solution with a metal salt and a reducing agent, and optionally additionally with a complexing agent and / or one or more auxiliaries. The metal salt can be a salt of Ag, Cu, Pd or Co. The term salt also includes complexes of metals or metal ions. The concentration of the metal salt may be in the range of 0.05-50 g / l, preferably 0.3-10 g / l, especially 0.4-2.0 g / l, based on the metal. When

Counteremergent or complexing agents include EDTA, Rochelle's salt, citric acid, citrates, tartaric acid, propionic acid, acetates, lactic acid, pyrophosphates, pyridium-3-sulfonic acid, tartrates, phosphates, borates, cyanides, thiocyanides, halides, triethylenetetram, and methylamine. In the case of the above salts, the counterions used can be, for example, Na ⁺ or K ⁺ . Suitable reducing agents are dextrose, glyoxal, Rochelle's salts, crystallized sugar, inverted sugar, co-ions, hydrides, glucams, metal hydrides,

Hydrazines, hydrazine sulfates, boranes, such as dimethylammborane, diethylamineborane, triethylammborane, formaldehyde, hypophosphites, gluconates, polyhydric alcohols, etc. Surface-active substances, in particular non-ionic, for example, are used as auxiliary agents

Ethylene glycol monomer units or nonylphenol ethoxylate, as well as commercially available agents, such as Ethylan 1008W, HB1, D253, CO35, CPG660, 1005, CD127P / N, A4, BCD42 or all agents sold under the name Berol (all from Akzo Nobel) , The surfactant may be present in concentrations of 0.01-10 g / l, especially 0.1-1.0 g / l, based on the total preparation. Also suitable as auxiliaries are polymers, such as polyethylene glycol having an average molecular weight of 100-4000. This can be done in concentrations of 0.01 - 10 g / l, especially 0.1 - 1.0 g / l, based on the preparation. Furthermore, inorganic or organic acids, such as boric acid, in amounts of 0.1 to 300 g / l, based on the preparation may be provided. Likewise, organic or inorganic bases, such as potassium, sodium, lithium,

Calcium, or magnesium hydroxide may be provided. These are then present in an amount which preferably adjusts the pH to 5.0-8.5, preferably 6.0-7.5, especially 6.0-7.2, especially 6.8-7.2. In the context of the invention, it is also possible to stabilize the pH value by means of suitable customary buffers. Concrete, suitable second compositions are otherwise described in the document WO 2006/065221 Al.

The step c) is preferably carried out a few ⁰ C, for example 2-5 ° C, below the tanning temperature of the second preparation. Preferred bath temperatures are above 20 ^° C., better above 30 ^° C., in particular above 50 ^° C. The bath temperature should expediently be below 100 ^° C., better below 80 ^° C.

The invention further relates to a conductive structure having a substrate which does not conduct the electrical current and to which an electrical current is arranged on the substrate and connected thereto

Conductive layer, wherein the conductive layer has a volume of the conductive layer by cross-metallic network, which is arranged in gaps between contained in the conductive layer electrically conductive or non-conductive particles, wherein the particles with each other and with the substrate via a associated organic binder. Such a conductive structure is obtainable, for example, by the process according to the invention.

The invention also includes a security and / or value document containing such a conductive structure, in particular designed as an RFID antenna.

All explanations in the context of the method according to the invention also apply analogously to the guide structure according to the invention or the security and / or value document according to the invention.

In the following, the invention will be explained in more detail with reference to an example representing only one embodiment.

Example 1: Comparative Example

With a screen printing machine were antenna structures

(HF-RFID antennas) printed on polycarbonate films of a thickness of 100 microns. The screen printing paste used was product 5029 from DuPont. This product contains metallic silver particles, an organic binder and an organic solvent. It was dried for 10 min. at 100 ^° C.

The antennas thus produced had a DC resistance of 30-35 ohms with a layer thickness of 20 microns. Example 2: Inventive example

First, an antenna structure according to Example 1 was made with the same materials and dimensions.

This antenna structure was then with a preparation according to the reference WO 2006/065221 at 70 ⁰ C, but a pH of 7.0 for 10 min. treated. Here, the layer thickness changed only insignificantly, a study of the cross-section showed that essentially also within the antenna structure, a deposition of silver had taken place.

A measurement of the resistance showed a reduction to 8 - 11 ohms.

For further electrical characterization, an RFID chip module was mounted on the antenna and the response field strength was measured as a function of the transmission rate. At a transmission rate of 424 kbit / s, 1.5 A / m were measured. This value corresponds to a value obtainable with a wire-wound antenna with the same module.

The adhesion of the antenna structure on the PC film corresponded to that of Example 1.

Claims

Claims:

1. A method for producing a for electrical

Current conductive layer on a substrate with the following process steps:

a) on the substrate, a coating of a first composition is applied, which contains an organic binder, - an aqueous or organic solvent and particles, b) the substrate with the coating is subjected to a drying process step, wherein the solvent is removed, c) the Substrate with the dried coating is treated with a second preparation for autocatalytic electroless metal plating.

2. The method of claim 1, wherein the substrate is an organic polymer, preferably selected from the group consisting of "PC (polycarbonate, especially bisphenol A polycarbonate), PET

(Polyethylene glycol terephthalate), PET-G, PET-F, PMMA (polymethyl methacrylate), ABS (acrylonitrile-butadiene-styrene), PE (polyethylene), PP (polypropylene), PI (polyimide or poly-trans-isoprene), PVC (polyvinyl chloride ) and copolymers of such polymers ". Method according to one of claims 1 or 2, wherein the substrate is a film or a foil composite of a security and / or value document, in particular an identity card, passport, ID card, access control card, visa, ticket, driver's note, motor vehicle paper, personalized security, a credit card, or personalized smart cards, is.

Method according to one of claims 1 to 3, wherein the conductive layer is an antenna structure, in particular an RFID circuit.

Method according to one of claims 1 to 4, wherein the coating by means of a printing process technique, in particular by screen printing, in step a) is applied.

Method according to one of claims 1 to 5, wherein the first preparation contains a proportion of solvent, preferably organic solvent, from 2 to 30% by weight, in particular 4 to 10 wt .-%, based on the total weight of the preparation.

7. The method according to any one of claims 1 to 6, wherein the first preparation comprises a proportion of 30 to 99 wt .-%, preferably 70 to 95 wt .-%, of particles, preferably electrically conductive particles, in particular metal particles, for example silver particles containing.

The method of any one of claims 1 to 7, wherein 90% of the particles by volume have a particle size in the range 0.1 to 30 μm.

9. The method according to any one of claims 1 to 8, wherein the stage b) for 0.1 to 100 mm., In particular 1 to 30 min., At 30 - 200 ⁰ C, in particular 60 to 130 ⁰ C, is performed.

10. The method according to any one of claims 1 to 9, wherein the second preparation is an aqueous solution with a metal salt and a reducing agent, and optionally additionally with a complexing agent and / or one or more excipients.

11. The method according to any one of claims 1 to 10, wherein the pH of the second preparation by means of adjuvants to 6.0 - 8.5, in particular 6, 0 - 7.3, preferably 6.8 - 7.2, is set , optionally by means of a buffer.

12. conductive structure with a non-conducting electrical current substrate and one on the substrate arranged and connected thereto conductive for electrical current conductive layer, wherein the conductive layer has a volume of the conductive layer by cross-metallic network, which is arranged in gaps between contained in the conductive layer electrically conductive or non-conductive particles, wherein the particles with each other and with the substrate via an organic binder, in particular obtainable according to one of claims 1 to 11.

13. Security and / or value document containing a lead structure according to claim 12.